Refrigerant composition

ABSTRACT

The present invention relates to a refrigerant composition of four-constituent system, comprising: (a) a first constituent of difluoromethane, (b) a second constituent of 1,1,1,2,3,3,3-heptafluoropropane, (c) a third constituent selected from the group consisting of 1,1,1,2-tetrafluoroethane and 1,1-difluoroethane and (d) a for the constituent selected from the group consisting of isobutane, 1,1,1,2,3,3,-hexafluoropropane and butane, useful as a substitute for chlorodifluoromethane (HCFC-22).

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a refrigerant composition useful as a refrigerant for a refrigerator, an air-conditioner, etc.

[0003] 2. Description of the Background Art

[0004] Chlorofluorocarbon (hereinafter referred to as “CFC”) compound, which were used as a refrigerant, have been restricted in production and use according to the Montreal Protocol because they have been found as a main factor in contributing to the destruction of the ozone layer in a stratosphere. In developed countries, the use of such CFC compounds have already been banned since 1996. It is also known that hydrochlorofluorocarbon (hereinafter referred to as “HCFC”) compounds such as HCFC-22 have considerable effects in causing damage to the ozone layer even though this effect is less severe than that of CFC compounds. For this reason, a restriction has been made to gradually reduce the use of HCFC compounds. A plan has also been made to ban the use of HCFC about 2030. In preparation of the full-scale restriction to the HCFC-22, many countries around the world are making a heavy investment to develop a refrigerant that can substitute HCFC-22.

[0005] However, it is well known that it is difficult to obtain a performance coefficient similar to that of HCFC-22 with a single material. One of methods to solve the above-mentioned problem would be to use of a mixed refrigerant having similar physical properties to that of HCFC-22.

[0006] Namely, a mixed refrigerant has advantages in that by controlling a composition of the mixed refrigerant, almost the same vapor pressure as the conventional refrigerant can be achieved, the same lubricant can be used, and the compressor needs not to be replaced. For this reason, several different types of mixed refrigerants have been developed as a substitute for HCFC-22 for the past several years.

[0007] Representative examples of a refrigerant composition developed as a substitute for HCFC-22 are HFC-407C and HFC-410A proposed by the American Society of Heating, Refrigerating and Air-conditioning Engineers (ASHRAE). HFC-407C is a refrigerant composition of HFC-32/125/134a in a ratio of 23/25/52 based on weight percent. Meanwhile, HFC-410A is a refrigerant composition of HFC-32/125 in a ratio of 50/50 based on weight percent.

[0008] In addition, U.S. Pat. No. 5,080,823 discloses a refrigerant composition of HFC-143a/propane, U.S. Pat. No. 5,211,867: HFC-125/143a, U.S. Pat. No. 5,234,613: HFC-32/propane, U.S. Pat. No. 5,236,611: PFC-218/HFC-143a, U.S. Pat. No. 5,290,466: HFC-32/134a/134, U.S. Pat. No. 5,340,490: HFC-23/CO₂ and HFC-23/116/CO₂, U.S. Pat. No. 5,403,504: HFC-125/32, U.S. Pat. No. 5,429,740: HFC-23/134a U.S. Pat. No. 5,538,660: HFC-32/HFC-134a/FC-41 and HFC-32/HFC-134a/PFC-218, and U.S. Pat. No. 5,643,492: HFC-32/125/134a.

[0009] Also, Japanese Patent Laid-open Publication No. 172386/1991 discloses a refrigerant composition of HFC-32/125/143a, Japanese Patent Laid-open Publication No. 170594/1991: HFC-23/125/134a, Japanese Patent Laid-open Publication No. 170593/1991: HFC-23/125/32, Japanese Patent Laid-open Publication No. 170591/1991: HFC-23/143a/134a, Japanese Patent Laid-open Publication No. 170590/1991: HFC-125/134a/32, Japanese Patent Laid-open Publication No. 170589/1991: HFC-23/143a/152a, Japanese Patent Laid-open Publication No. 170588/1991: HFC-125/143a/134a, Japanese Patent Laid-open Publication No. 170585/1991: HFC-32/125/134a, Japanese Patent Laid-open Publication No. 170584/1991: HFC-23/134a/152a, Japanese Patent Laid-open Publication No. 170583/1991: HFC-1251143a/32, Japanese Patent Laid-open Publication No. 222893/1992: HFC-32/125, Japanese Patent Laid-open Publication No. 154887/1992: HFC-134/152a, Japanese Patent Laid-open Publication No. 117645/1993: HFC-23/134a/propane, Japanese Patent Laid-open Publication No. 117643/1993: HFC-125/134a/propane, Japanese Patent Laid-open Publication No. 65561 /1994: HFC-23/152a/,PFC-218, Japanese Patent Laid-open Publication No. 128872/1994: HFC-32/PFC-218, Japanese Patent Laid-open Publication No. 220433/1994: HFC-32/125/RC-318, Japanese Patent Laid-open Publication No. 173462/1995: HFC-143a/125/134a/heptane, Japanese Patent Laid-open Publication No. 176537/1996: PFC-218/RC-270/HFC-152a, Japanese Patent Laid-open Publication No. 151569/1996: propane/RC-270/HFC-134a, Japanese Patent Laid-open Publication No. 127767/1996: HFC-32/134a/RC-318, Japanese Patent Laid-open Publication No. 25480/1997: HFC-32/134a/125/isobutane, Japanese Patent Laid-open Publication No. 59611/1997: HFC-134a/isobutane, Japanese Patent Laid-open Publication No. 208941/1997: HFC-32/152a/125/RC-270, and Japanese Patent Laid-open Publication No. 221664/1997: HFC-125/143a/134a/RC-270.

[0010] Also, Korean Patent Laid-open Publication No. 91-9902 discloses a refrigerant composition of HFC-23/32/152a, HFC-23/125/152a, HFC-32/143a/152a, HFC-125/143a/152a, HFC-32/125/125a and HFC-23/143a/152a, Korean Patent Laid-open Publication No. 91-9903: HFC-23/32/134, HFC-23/32/134a, HFC-23/125/134, HFC-32/125/134, HFC-23/143a/134a, HFC-125/143a/134a and HFC-125/143a/134, Korean Patent Laid-open Publication No. 96-4485: HFC-32/23/134a, Korean Patent Laid-open Publication No. 96-701168: HFC- 227ea/HFC-152a, and Korean Patent Laid-open Publication No. 97-704853: HFC-134a/HCFC-124/butane.

[0011] Such various types of mixed refrigerants as mentioned above are being applied to a refrigerator, an air-conditioner, etc.

SUMMARY OF THE INVENTION

[0012] Therefore, an object of the present invention is to provide a refrigerant composition which has a novel composition, exhibits a similar performance to that of HCFC-22, has no possibility of damaging the ozone layer, and accordingly can be used as a substitute for HCFC-22.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] To achieve the above and other objects of the present invention, as embodied and broadly described herein, there is provided a refrigerant composition of four-constituent system, comprising: (a) a first constituent of difluoromethane (hereinafter referred to as “HFC-32”), (b) a second constituent of 1,1,1,2,3,3,3-heptafluoropropane (hereinafter referred to as “HFC-227ea”), (c) a third constituent selected from the group consisting of 1,1,1,2-tetrafluoroethane (hereinafter referred to as “HFC-134a”) and 1,1-difluoroethane (hereinafter referred to as “HFC-152a”), and (d) a forth constituent selected from the group consisting of isobutane (hereinafter referred to as “R-600a”), 1,1,1,2,3,3,- hexafluoropropane (hereinafter referred to as “HFC-236ea”) and butane (hereinafter referred to as “R-600”).

[0014] That is, the refrigerant composition of the present invention comprises (a) a first constituent of HFC-32, (b) a second constituent of HFC-227ea as a second constituent, (c) a third constituent selected from the group consisting of HFC-134a and HFC-152a, and (d) a forth constituent selected from the group consisting of R-600a, HFC-236ea and R-600.

[0015] First, the composition of a refrigerant composition of the present invention containing HFC-32, HFC-227ea, HFC-134a, and one constituent selected from the group consisting of R-600a, HFC-236ea and R-600 will now be described.

[0016] In a refrigerant composition according to one embodiment of the present invention, the contents of HFC-32, HFC-227ea, HFC-134a and R-600a are preferably in the range of 50-60 wt. %, 10-20 wt. %, 10-30 wt. % and 5-15 wt. %, respectively, to the total weight of the refrigerant composition. And more preferably, the contents of HFC-32, HFC-227ea, HFC-134a and R-600a are in the range of 53-57 wt. %, 13-17 wt. %, 15-25 wt. % and 8-12 wt. %, respectively.

[0017] In a refrigerant composition according to another embodiment of the present invention, the contents of HFC-32, HFC-227ea, HFC-134a and HFC-236ea are preferably in the range of 50-70 wt. %, 10-20 wt. %, 10 -30 wt.% and 5 -15 wt.%, respectively, to the total weight of the refrigerant composition. And more preferably, the contents of HFC-32, HFC-227ea, HFC-134a and HFC-236ea are in the range of 55-65 wt. %, 13-17 wt. %, 15-25 wt. % and 7-12 wt. %, respectively.

[0018] In a refrigerant composition according to another embodiment of the present invention, the contents of HFC-32, HFC-227ea, HFC-134a and R-600 are preferably in the range of 50-70 wt. %, 10-20 wt. %, 10-30 wt. % and 5-12 wt. %, respectively, to the total weight of the refrigerant composition. And more preferably, the contents of HFC-32, HFC-227ea, HFC-134a and R-600 are in the range of 55-65 wt. %, 13-17 wt. %, 15-25 wt. % and 7-10 wt. %, respectively.

[0019] Next, the composition of a refrigerant composition comprising HFC-32, HFC-227ea, HFC-152a, and one constituent selected from the group consisting of R-600a, HFC-236ea and R-600 will now be described.

[0020] In a refrigerant composition according to one embodiment of the present invention, the contents of HFC-32, HFC-227ea, HFC-152a and R-600a are preferably in the range of 40-70 wt. %, 10-20 wt. %, 10-40 wt. % and 5-15 wt. %, respectively, to the total weight of the refrigerant composition. And more preferably, the contents of HFC-32, HFC-227ea, HFC-1 52a and R-600a are in the range of 50-60 wt. %, 13-17 wt. %, 20-30 wt. % and 7-12 wt. %, respectively.

[0021] In a refrigerant composition according to another embodiment of the present invention, the contents of HFC-32, HFC-227ea, HFC-152a and HFC-236ea are preferably in the range of 50-70 wt. %, 10-20 wt. %, 10-30 wt. % and 5-15 wt. %, respectively, to the total weight of the refrigerant composition. And more preferably, the contents of HFC-32, HFC-227ea, HFC-152a and HFC-236ea are in the range of 55 -65 wt.%, 13 -17 wt.%, 15 -25 wt.% and 7 -12 wt.%, respectively.

[0022] In a refrigerant composition according to another embodiment of the present invention, the contents of HFC-32, HFC-227ea, HFC-152a and R-600 are preferably in the range of 40-70 wt. %, 10-20 wt. %, 10-40 wt. % and 5-12 wt. %, respectively, to the total weight of the refrigerant composition. And more preferably, contents of HFC-32, HFC-227ea, HFC-152a and R-600 are in the range of 50-60 wt. %, 13-17 wt. %, 20-30 wt. % and 7-10 wt. %, respectively.

[0023] The refrigerant composition of the present invention as described above exhibits the similar performance to that of the conventional HCFC-22 (see Table 10). Further, because there is no risk to damage the ozone layer, there is no concern to be restricted in its use in the future, and thereby, it can be used as a substitute for HCFC-22.

EXAMPLE

[0024] The present invention will now be described in more detail in the following examples. However, it is to be understood that these examples are merely illustrative and it is not intended to limit the scope of the present invention to these examples.

1. Preparation of a Refrigerant Composition Examples 1-6 Composition of HFC-32/HFC-134a/HFC-227ea/R-600a

[0025] Refrigerant compositions having the composition shown in Table 1 were prepared by mixing the constituents according to the typical method. TABLE 1 Example Mixed refrigerant composition (wt. %) No. HFC-32 HFC-134a HFC-227ea R-600a 1 50 20 20 10 2 50 30 10 10 3 60 10 20 10 4 60 20 10 10 5 50 25 20  5 6 55 15 15 15

Examples 7-12 Composition of HFC-32/HFC-134a/HFC-227ea/HFC-236ea

[0026] Refrigerant compositions having the composition shown in Table 2 were prepared by mixing the constituents according to the typical method. TABLE 2 Example Mixed refrigerant composition (wt. %) No. HFC-32 HFC-134a HFC-227ea HFC-236ea  7 50 30 10 10  8 60 10 20 10  9 60 20 10 10 10 70 10 10 10 11 60 20 15  5 12 60 15 10 15

Examples 13-18 Composition of HFC-32/HFC-134a/HFC-227ea/R-600

[0027] Refrigerant compositions having the composition shown in Table 3 were prepared by mixing the constituents according to the typical method. TABLE 3 Example Mixed refrigerant composition (wt. %) No. HFC-32 HFC-134a HFC-227ea R-600 13 50 30 10 10 14 60 10 20 10 15 60 20 10 10 16 70 10 10 10 17 60 20 15  5 18 62 16 10 12

Examples 19-26 Composition of HFC-32/HFC-152a/HFC-227ea/R-600a

[0028] Refrigerant compositions having the composition shown in Table 4 were prepared by mixing the constituents according to the typical method. TABLE 4 Example Mixed refrigerant composition (wt. %) No. HFC-32 HFC-152a HFC-227ea R-600a 19 40 40 10 10 20 50 20 20 10 21 50 30 10 10 22 60 10 20 10 23 60 20 10 10 24 70 10 10 10 25 50 30 15  5 26 60 15 10 15

Examples 27-33 Composition of HFC-32/HFC-152a/HFC-227ea/HFC-236ea

[0029] Refrigerant compositions having the composition shown in Table 5 were prepared by mixing the constituents according to the typical method. TABLE 5 Example Mixed refrigerant composition (wt. %) No. HFC-32 HFC-152a HFC-227ea HCF-236ea 27 50 20 20 10 28 50 30 10 10 29 60 10 20 10 30 60 20 10 10 31 70 10 10 10 32 55 25 15  5 33 60 15 10 15

Examples 34-40 Composition of HFC-32/HFC-152a/HFC-227ea/R-600

[0030] Refrigerant compositions having the composition shown in Table 6 were prepared by mixing the constituents according to the typical method. TABLE 6 Example Mixed refrigerant composition (wt. %) No. HFC-32 HFC-152a HFC-227ea R-600 34 40 40 10 10 35 50 30 10 10 36 60 10 20 10 37 60 20 10 10 38 70 10 10 10 39 55 25 15  5 40 62 16 10 12

Comparative Examples 1-6

[0031] Refrigerant compositions having the composition shown in Table 7 were prepared by mixing the constituents according to the typical method. These mixtures contain the same constituents as in the Examples 1-18 but with different contents of some constituents. TABLE 7 Com- para- tive Exam- Mixed refrigerant composition (wt. %) ple No. HFC-32 HFC-134a HFC-227a R-600a HFC-236a R-600 1 20 30 20 30 — — 2 50 10 30 10 — — 3 20 30 20 — 30 — 4 50 10 30 — 10 — 5 20 30 20 — — 30 6 50 10 30 — — 10

Comparative Examples 7-12

[0032] Refrigerant compositions having the composition shown in Table 8 were prepared by mixing the constituents according to the typical method. These mixtures contain the same constituents as in the Examples 19-40 but with different contents of some constituents. TABLE 8 Com- para- tive Exam- Mixed refrigerant composition (wt. %) ple No. HFC-32 HFC-152a HFC-227a R-600a HFC-236a R-600  7 20 30 20 30 — —  8 50 10 30 10 — —  9 20 30 20 — 30 — 10 50 10 30 — 10 — 11 20 30 20 — — 30 12 50 10 30 — — 10

Comparative Examples 13-15

[0033] Conventional refrigerants of HCFC-22, HFC-407C and HFC-410A having the composition as shown in Table 9 were respectively prepared by mixing the constituents according to the typical method. TABLE 9 Comparative Examples Mixed refrigerator composition (wt. %) No. HCFC-22 HFC-32 HFC-125 HFC-134a Refrigerant 13 100 — — — HCFC-22 14 — 23 25 52 HFC-407C 15 — 50 50 — HFC-410A

2. Performance Test of the Refrigerant Composition

[0034] The refrigerant compositions prepared as in Examples 1 through 40 and the Comparative Examples 1 through 12 were applied to a refrigeration system which comprises a compressor, a condenser, an expansion valve and an evaporator. And then, main factors for evaluating refrigerant performance such as a coefficient of performance (COP), a volumetric capacity (VC) of the refrigerant, pressure in the condenser (P_(H)) and pressure in the evaporator (P_(L)) were measured under the following conditions:

[0035] Refrigeration capacity: 2 kW

[0036] Coefficient of Overall Heat Transfer in Evaporator (UA): 0.20 kW/K

[0037] Coefficient of Overall Heat Transfer in Condenser (UA): 0.20 kW/K

[0038] Degree of Subcooling in Condenser: 5° C.

[0039] Degree of Superheating in Evaporator: 5° C.

[0040] Efficiency of Compressor: 0.8

[0041] Temperature of Secondary Fluid at Inlet of Condenser: 25° C

[0042] Temperature of Secondary Fluid at Outlet of Condenser: 35° C

[0043] Temperature of Secondary Fluid at Inlet of Evaporator: 15° C

[0044] Temperature of Secondary Fluid at Outlet of Evaporator: 5° C

[0045] Table 10 shows the performance test results of the refrigerant compositions of Examples 1-40. TABLE 10 Example VC P_(L) P_(H) No. COP (kJ/m³) (kPa) (kPa)  1 5.05 4429.7 635.0 1829.1  2 5.11 4394.8 623.6 1788.4  3 5.17 4862.6 703.1 1947.8  4 5.21 4800.4 686.1 1900.6  5 5.10 4366.3 609.5 1776.9  6 4.99 4557.0 666.7 1900.5  7 5.03 4001.8 535.9 1643.5  8 5.11 4516.4 620.4 1817.6  9 5.15 4415.7 597.8 1754.9 10 5.31 4839.9 661.6 1856.0 11 5.21 4514.7 613.5 1775.2 12 5.03 4332.2 589.0 1768.4 13 5.00 4093.8 569.1 1700.6 14 5.00 4512.9 642.7 1866.3 15 5.10 4498.0 632.1 1816.9 16 5.23 4908.9 696.6 1923.1 17 5.22 4609.0 639.4 1817.5 18 4.98 4456.5 632.3 1843.7 19 5.00 3532.6 478.1 1466.0 20 5.03 4134.1 578.8 1706.9 21 5.04 3959.8 544.6 1621.4 22 5.14 4678.3 668.0 1879.2 23 5.13 4436.3 620.5 1776.6 24 5.27 4976.2 708.0 1933.8 25 5.07 3911.6 528.2 1588.0 26 5.07 4530.4 649.5 1843.3 27 5.02 3882.8 519.0 1599.7 28 5.06 3717.8 488.5 1509.3 29 5.12 4398.9 599.1 1761.7 30 5.14 4168.3 556.5 1655.4 31 5.28 4680.7 635.1 1801.1 32 5.13 3993.5 530.4 1595.0 33 5.05 4188.0 563.4 1696.7 34 5.02 3430.5 459.3 1419.0 35 5.05 3839.0 522.2 1569.9 36 5.04 4434.2 625.6 1814.1 37 5.12 4290.4 593.4 1719.8 38 5.24 4794.3 674.4 1870.4 39 5.12 4077.1 552.4 1637.3 40 5.06 4353.5 609.2 1766.9

[0046] Table 11 shows the performance test results of the refrigerant compositions of Comparative Examples 1-12. TABLE 11 Comparative Example VC P_(L) P_(H) No. COP (kJ/m³) (kPa) (kPa)  1 4.26 2697.9 390.8 1389.2  2 4.94 4416.4 639.8 1870.2  3 4.21 2337.6 300.1 1249.6  4 4.86 4104.4 565.2 1759.6  5 3.89 2129.4 288.5 1249.9  6 4.77 4085.8 582.1 1794.6  7 4.52 2663.9 373.4 1271.6  8 4.96 4278.1 611.5 1802.0  9 4.53 2397.6 305.4 1153.5 10 4.92 4026.3 549.2 1701.4 11 4.18 2233.6 301.4 1179.3 12 4.83 4031.2 569.1 1743.7

[0047] Table 12 shows the performance test results of the refrigerant compositions of Comparative Examples 13-15. TABLE 12 Comparative Example VC P_(L) P_(H) No. COP (kJ/m³) (kPa) (kPa) 13 4.26 2697.9 390.8 1389.2 14 4.94 4416.4 639.8 1870.2 15 4.21 2337.6 300.1 1249.6

[0048] As shown in Tables 10 and 12, the performances as indicated in each item of the refrigerant compositions of Examples 1-40 are similar to those of the conventional refrigerants of HCFC-22, HFC-407C and HFC-410A. Accordingly, the refrigerant compositions of Examples 1 through 40 can be used as a substitute for the HCFC-22.

[0049] However, the refrigerant compositions of Comparative Examples 1 through 12 exhibit poor performances compared to the refrigerants of Examples 1 through 40 according to the present invention, and therefore, it is discovered that they are inappropriate to use as a substitute for HCFC-22. 

What is claimed is:
 1. A refrigerant composition, comprising: (a) a first constituent of difluoromethane, (b) a second constituent of 1,1,1,2,3,3,3-heptafluoropropane, (c) a third constituent selected from the group consisting of 1,1,1,2-tetrafluoroethane and 1,1-difluoroethane, and (d) a forth constituent selected from the group consisting of isobutane, 1,1,1,2,3,3-hexafluoropropane and butane.
 2. The refrigerant composition according to claim 1, wherein the content of the difluoromethane is 50-70 wt. %, the content of the 1,1,1,2,3,3,3-heptafluoropropane is 10-20 wt. %, the content of the 1,1,1,2-tetrafluoroethane is 10-30 wt. %, and the content of the forth constituent selected from the group consisting of isobutane, 1,1,1,2,3,3-hexafluoropropane and butane is 5-15 wt. %.
 3. The refrigerant composition according to claim 2, wherein the content of the difluoromethane is 50-60 wt. %.
 4. The refrigerant composition according to claim 2, wherein the content of butane is 5-12 wt. %.
 5. The refrigerant composition according to claim 1, wherein the content of the difluoromethane is 40-70 wt. %, the content of 1,1,1,2,3,3,3-heptafluoropropane is 10-20 wt. %, the content of 1,1-difluoroethane is 10-40 wt. %, and the content of the forth constituent selected from the group consisting of isobutane, 1,1,1,2,3,3-hexafluoropropane and butane is 5-15 wt. %.
 6. The refrigerant composition according to claim 5, wherein the content of difluoromethane is 50-70 wt. % and a content of 1,1-difluoroethane is 10-30 wt. %.
 7. The refrigerant composition according to claim 5, wherein the content of butane is 5-12 wt. %. 